The structural anisotropy of various poly(alkylthiophene) films have been studied by X-ray diffraction, using both conventional methods and synchrotron radiation at grazing incidence. Solution-cast films orient with the side chains preferably normal to the film surface, whereas spin-cast films of nonstereoregular material orient with both the main and the side chains in the film plane. For thick (10-50 µm) solution-cast films, the degree of orientation depends strongly on the solvent used for casting, and on the stereoregularity of the polymer, films of stereoregular materials being more oriented than those of nonregular materials. The most oriented nonregular films are those cast from mixtures of chloroform and tetrahydrofuran. Thin (50-500 nm) solution-cast films are more oriented than the thicker ones, and the effects of different stereoregularity or different casting solvents are small. For spin-cast films, the degree of orientation is independent of substrate and solvent. Spin-cast films of stereoregular material have two different phases: One with the side chains normal to the substrate, and another where they are parallel to the substrate. The diffraction peaks of spin-cast poly(octylthiophene) narrow considerably upon heating.

Electrochemical dedoping and redoping of p-toluene sulfonate doped poly(3,4-ethylenedioxythiophene) (PEDOT) has been studied with in situ grazing incidence diffraction with water used as an electrolyte. The diffraction peak positions and integrated intensities do not change significantly during doping and dedoping, while the peak widths increase upon dedoping and decrease upon doping. This implies that the lattice parameters and the relative positions of the polymer chains and the p-toluene sulfonate ions remain unchanged, the redox processes being carried out by the motion of smaller ions between the polymer and the electrolyte, and that the structural order decreases upon dedoping and increases upon doping in a reversible manner.

Various substituted poly(phenylthiophene)s have been studied by X-ray diffraction. They are semicrystalline, with very different degrees of crystallinity. Those with para-substituted phenyl groups have a low degree of crystallinity, whereas those with ortho-substituted phenyl groups are more crystalline. The most crystalline materials in this study have two equally long substituents on the phenyl ring, one at the ortho position and the other at the ortho or meta position on the opposite side of the phenyl ring. Poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT) was most thoroughly studied, and a structural model is proposed. The structure of PDOPT is quite different from previously studied substituted polythiophenes in that the octyl side chains are directed normal to the thiophene planes. In this way, the conjugated polymer chains are kept separated from each other. Solution-cast and spin-cast PDOPT films are anisotropic, with the octyl side chains oriented normal to the film surface in both cases. This is contrary to the situation for poly(3-alkylthiophene)s, where solution-cast and spin-cast films orient in different ways.

Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we describe ultrafast charge separation at the interface of a conjugated polymer and an aggregate of the fullerene derivative PCBM using the stochastic Schrodinger equation (SSE) and reveal the complex time evolution of electron transfer, mediated by electronic coherence and delocalization. By fitting the model to ultrafast charge separation experiments, we estimate the extent of electron delocalization and establish the transition from coherent electron propagation to incoherent hopping. Our results indicate that even a relatively weak coupling between PCBM molecules is sufficient to facilitate electron delocalization and efficient charge separation at organic interfaces.

Powering the future, while maintaining a cleaner environment and a strong socioeconomic growth, is going to be one of the biggest challenges faced by mankind in the 21st century. The first step in overcoming the challenge for a sustainable future is to use energy more efficiently so that the demand for fossil fuels can be reduced drastically. The second step is a transition from the use of fossil fuels to renewable energy sources. In this sense, organic electrode materials are becoming increasingly attractive compared to inorganic electrode materials which have reached a plateau regarding performance and have severe drawbacks in terms of cost, safety and environmental friendliness. Using organic composites based on conducting polymers, such as polypyrrole, and abundant, cheap and naturally occurring biopolymers rich in quinones, such as lignin, has recently emerged as an interesting alternative. These materials, which exhibit electronic and ionic conductivity, provide challenging opportunities in the development of new charge storage materials. This review presents an overview of recent developments in organic biopolymer composite electrodes as renewable electroactive materials towards sustainable, cheap and scalable energy storage devices.

A ternary composite supercapacitor electrode consisting of phosphomolybdic acid (HMA), a renewable biopolymer, lignin, and polypyrrole was synthesized by a simple one-step simultaneous electrochemical deposition and characterized by electrochemical methods. It was found that the addition of HMA increased the specific capacitance of the polypyrrole-lignin composite from 477 to 682 F g(-1) ( at a discharge current of 1 A g(-1)) and also significantly improved the charge storage capacity from 6(to 128 mA h g(-1).

New solution-processable, anthrancene- and benzothiadiazole-containing polyfluorene copolymers (P1-P3) have been synthesized and characterized. The preparation and characterization of the corresponding blue light-emitting devices are also reported. Polymers P2 and P3 show high photoluminescence efficiency while polymer P2 does not show any significant light emission up to 8.0 V. The results show the need for balance of electron and hole transport in polymer light emitting diodes.

The electrochemical and charge storage properties of different lignins inside biopolymer electrodes were studied and correlated with the chemical variations of the lignins as indicated from the nuclear magnetic resonance (NMR) spectroscopic data. The varying fractions of monolignols were found to correlate with charge storage properties. It was found that as the sinapyl to guaiacyl (S/G) ratio increased both the specific capacitance and charge capacity increased considerably. This indicates that quinones generated on S-units can contribute more to charge storage in the biopolymer electrodes.

This paper presents the work carried out within the European project RENAISSANCE-ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications. Within the project different types of innovative polyelectrolytes were synthesized such as poly(ionic liquid)s coming from renewable or natural ions, thiazolium cations, catechol functionalities or from a new generation of cheap deep eutectic monomers. Further, macromolecular architectures such as new poly(ionic liquid) block copolymers and new (semi)conducting polymer/polyelectrolyte complexes were also developed. As the final goal, the application of these innovative polymers in energy and the environment was investigated. Important advances in energy storage technologies included the development of new carbonaceous materials, new lignin/conducting polymer biopolymer electrodes, new iongels and single-ion conducting polymer electrolytes for supercapacitors and batteries and new poly(ionic liquid) binders for batteries. On the other hand, the use of innovative polyelectrolytes in sustainable environmental technologies led to the development of new liquid and dry water, new materials for water cleaning technologies such as flocculants, oil absorbers, new recyclable organocatalyst platforms and new multifunctional polymer coatings with antifouling and antimicrobial properties. All in all this paper demonstrates the potential of poly(ionic liquid)s for high-value applications in energy and enviromental areas. (c) 2017 Society of Chemical Industry

Developing sustainable organic electrode materials for energy storage applications is an urgent task. We present a promising candidate based on the use of lignin, the second most abundant biopolymer in nature. This polymer is combined with a conducting polymer, where lignin as a polyanion can behave both as a dopant and surfactant. The synthesis of PEDOT/Lig biocomposites by both oxidative chemical and electrochemical polymerization of EDOT in the presence of lignin sulfonate is presented. The characterization of PEDOT/Lig was performed by UV-Vis-NIR spectroscopy, FTIR infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry and galvanostatic charge-discharge. PEDOT doped with lignin doubles the specific capacitance (170.4 F g(-1)) compared to reference PEDOT electrodes (80.4 F g(-1)). The enhanced energy storage performance is a consequence of the additional pseudocapacitance generated by the quinone moieties in lignin, which give rise to faradaic reactions. Furthermore PEDOT/Lig is a highly stable biocomposite, retaining about 83% of its electroactivity after 1000 charge/discharge cycles. These results illustrate that the redox doping strategy is a facile and straightforward approach to improve the electroactive performance of PEDOT.

We report spectroelectrochemical studies to investigate the charge storage mechanism of composite polypyrrole/lignin electrodes. Renewable bioorganic electrode materials were produced by electropolymerization of pyrrole in the presence of a water-soluble lignin derivative acting as a dopant. The resulting composite exhibited enhanced charge storage abilities due to a lignin-based faradaic process, which was expressed after repeated electrochemical redox of the material. The in situ FTIR spectroelectrochemistry results show the formation of quinone groups, and reversible oxidation-reduction of these groups during charge-discharge experiments in the electrode materials. The most significant IR bands include carbonyl absorption near 1705 cm(-1), which is attributed to the creation of quinone moieties during oxidation, and absorption at 1045 cm(-1) which is due to hydroquinone moieties.

Daily and seasonally fluctuating energy supply and demand requires adequate energy storage solutions. In recent years electrochemical supercapacitors have attracted considerable attention due to their ability to both store and deliver electrical energy efficiently. Our efforts are focused on developing and optimizing sustainable organic electrode materials for supercapacitors based on renewable bioorganic materials, offering a cheap, environmentally friendly and scalable alternative to store energy. In particular, we are using the second most abundant biopolymer in nature, lignin (Lig), which is an insulating material. However, when used in combination with electroactive and conducting polymers such as polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT), the biohybrid electrodes PPy/Lig and PEDOT/Lig display significantly enhanced energy storage performance as compared to the pristine conducting polymers without the lignin. Redox cyclic voltammetry and galvanostatic charge/discharge measurements indicate that the enhanced performance is due to the additional pseudocapacitance generated by the quinone moieties in lignin. Moreover, a conjugated redoxpolymer poly(aminoanthraquinone) PAAQ, with intrinsic quinone functions and excellentstability, has been combined with lignin and PEDOT resulting in a trihybrid bioelectrode. PEDOT compensates the low conductivity of PAAQ and provides electrical pathways to the quinone groups. The electrochemically generated quinones undergo a two electron, two protonredox process within the biohybrid electrodes as revealed by FTIR spectroelectrochemistry.These remarkable features reveal the exciting potential of a full organic energy storage device with long cycle life. Therefore, supercapacitor devices were designed in symmetric or asymmetric two electrode configuration. The best electrochemical performance was achieved by the asymmetric supercapacitor based on PEDOT+Lignin/PAAQ as the positive electrode and PEDOT/PAAQ as the negative electrode. This device exhibits superior electrochemical performance and outstanding stability after 10000 charge/discharge cycles due to the synergistic effect of the two electrodes. Finally, we have characterized the response of this supercapacitor device when charged with the intermittent power supply from an organic photovoltaic module. We have designed charging/discharging conditions such that reserve power was available in the storage device at all times. This work has resulted in an inexpensive fully organic system witht he dual function of energy conversion and storage.

Abstract [en]

Powering the future, while maintaining a cleaner environment and a strong socioeconomic growth, is going to be one of the biggest challenges faced by mankind in the 21st century. The first step in overcoming the challenge for a sustainable future is to use energy more efficiently so that the demand for fossil fuels can be reduced drastically. The second step is a transition from the use of fossil fuels to renewable energy sources. In this sense, organic electrode materials are becoming increasingly attractive compared to inorganic electrode materials which have reached a plateau regarding performance and have severe drawbacks in terms of cost, safety and environmental friendliness. Using organic composites based on conducting polymers, such as polypyrrole, and abundant, cheap and naturally occurring biopolymers rich in quinones, such as lignin, has recently emerged as an interesting alternative. These materials, which exhibit electronic and ionic conductivity, provide challenging opportunities in the development of new charge storage materials. This review presents an overview of recent developments in organic biopolymer composite electrodes as renewable electroactive materials towards sustainable, cheap and scalable energy storage devices.

Abstract [en]

We report spectroelectrochemical studies to investigate the charge storage mechanism of composite polypyrrole/lignin electrodes. Renewable bioorganic electrode materials were produced by electropolymerization of pyrrole in the presence of a water-soluble lignin derivative acting as a dopant. The resulting composite exhibited enhanced charge storage abilities due to a lignin-based faradaic process, which was expressed after repeated electrochemical redox of the material. The in situ FTIR spectroelectrochemistry results show the formation of quinone groups, and reversible oxidation-reduction of these groups during charge-discharge experiments in the electrode materials. The most significant IR bands include carbonyl absorption near 1705 cm(-1), which is attributed to the creation of quinone moieties during oxidation, and absorption at 1045 cm(-1) which is due to hydroquinone moieties.

Place, publisher, year, edition, pages

ROYAL SOC CHEMISTRY, 2015

National Category

Materials Chemistry

Identifiers

Note

Funding Agencies|Knut and Alice Wallenberg foundation; Marie Curie network Renaissance; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]

Abstract [en]

Developing sustainable organic electrode materials for energy storage applications is an urgent task. We present a promising candidate based on the use of lignin, the second most abundant biopolymer in nature. This polymer is combined with a conducting polymer, where lignin as a polyanion can behave both as a dopant and surfactant. The synthesis of PEDOT/Lig biocomposites by both oxidative chemical and electrochemical polymerization of EDOT in the presence of lignin sulfonate is presented. The characterization of PEDOT/Lig was performed by UV-Vis-NIR spectroscopy, FTIR infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry and galvanostatic charge-discharge. PEDOT doped with lignin doubles the specific capacitance (170.4 F g(-1)) compared to reference PEDOT electrodes (80.4 F g(-1)). The enhanced energy storage performance is a consequence of the additional pseudocapacitance generated by the quinone moieties in lignin, which give rise to faradaic reactions. Furthermore PEDOT/Lig is a highly stable biocomposite, retaining about 83% of its electroactivity after 1000 charge/discharge cycles. These results illustrate that the redox doping strategy is a facile and straightforward approach to improve the electroactive performance of PEDOT.

The charge carrier dynamics of a new polymer-fullerene blend are examined on the femtosecond to the millisecond time scale. The full time range is globally fitted using a chemical reaction rate model that includes all key processes, charge generation, energy transfer, charge separation, and recombination, over the full 12 orders of magnitude in time and a factor of 33 in light intensity. Particular attention is paid to the charge recombination processes and it is found that they are highly material specific. Comparison of the dynamics to those of a previously studied polymer: fullerene blend reveals that while for one blend the recombination dynamics are mainly controlled by geminate recombination, the charge recombination in the presently studied polymer: fullerene blend are entirely controlled by non-geminate electron-hole recombination. Carrier density dependence of the non-geminate recombination rate is analyzed and a correlated disorder model of site energies is proposed to explain the observed dependency.

Mobility versus temperature measurements on two different polymer: fullerene blends intended for solar cell applications have been evaluated in terms of the energetic disorder and how this varies with stoichiometry. The charge transport is shown to be confined to the intended phases in both cases, but with fundamentally different interaction properties. In one case the energetic disorder is a function of stoichiometry for the hole transport, while it is constant and equal to that of the pure fullerene for electrons, and in the other case it is the hole transport that has a stoichiometry independent energetic disorder. Transport site dilution is argued to be present in the fixed energetic disorder system and this is offered as a partial explanation to molecular weight dependent currents in solar cells. Determination of the glass transition temperature through the use of field effect transistors is also demonstrated.

The main topic of this dissertation is electronic charge transport in polymeric and molecular organic materials and material blends intended for solar cell applications. Charge transport in polymers is a strange beast and carrier mobility is rarely a well-defined number. Measurements on different sample geometries and under different conditions tend to give different results and when everything is to be related to solar cell performance it is imperative that there is a way to correlate the results from different measurements. Polymer solar cells utilize composite materials for their function. This puts an additional twist on charge transport studies, as there will also be interaction between the different phases to take into account.

Several measurement techniques have been used and their interrelationships as well as information on their relevance for solar cells have been investigated. Field effect transistors (FET) with an organic active layer have proved to be one of the more versatile measurement geometries and are also an interesting topic in itself. FETs are discussed both as a route for material characterization and as components. A main result correlates bias stress in organic field effect transistors with the electronic structure of the material.

Power conversion efficiency in solar cells is discussed with respect to electrical properties. The interaction of different blend materials and the impact of stoichiometry on transport properties in the active layer have been investigated. Results indicate that charge transport properties frequently are a key determining factor for which material combinations and ratios that works best.

Some work on the conductive properties of nano-fibers coated with semiconducting polymers has also been done and is briefly discussed. The conductive properties of nano-fibers have been studied through potential imaging.

Abstract [en]

Non-ideal behavior in organic field effect transistors, in particular threshold voltage drift and light sensitivity, is argued to be due to intrinsic carrier dynamics. The discussion is based on the theory for hopping transport within a Gaussian density of states. Carrier concentration is shown to be of fundamental importance, and the time required to reach equilibrium at different bias is responsible for device behavior, with implications for mobility evaluation. Experimental results from various conjugated polymers in a field effect transistor illustrate the theory.

Abstract [en]

Bothelectron and hole mobilities have been simultaneously measured through chargeextraction by linearly increasing voltage on polymer heterojunction solar cellswith varying stoichiometry of polymer and acceptor. The polymer isa low band gap copolymer of fluorene, thiophene, and electronaccepting groups named APFO-Green 5, and the acceptor is [6,6]-phenyl-C61-butyricacid methylester. Results are correlated to field effect transistor measurementson the same material system. A monotonous increase in mobilityfor both carrier types is observed with increased acceptor loading.

Abstract [en]

Bipolartransport in blends of a copolymer of fluorene, thiophene andelectron accepting groups, and the substituted fullerene [6,6]-phenyl-C61-butyric acid methylesterhave been studied through charge extraction by linearly increasing voltageon solar cells and with field effect transistors. Between 10%and 90% polymer has been used and the results showa clear correlation to solar cell performance. Optimal solar cellscomprise 20% polymer and have a power conversion efficiency of3.5%. The electron mobility is increasing strongly with fullerene content,but is always lower than the hole mobility, thus explainingthe low amount of polymer in optimized devices.

Abstract [en]

Holemobility in polyfluorene/fullerene blends has been studied with field effecttransistors. Two different C60 derivatives and one C70 derivative havebeen investigated together with two different polyfluorenes. Mobility is presentedas a function of acceptor loading at ratios suitable forphotovoltaics and varies between 10–3 and 10–5 cm2 V–1 s–1 depending on thepolymer/acceptor combination. The hole mobility is increased in blends withthe commonly used acceptor [6-6]-phenyl-C61-butyric acid methylester (PCBM). With relatedC60 and C70 derivatives the hole mobility is decreased underthe same circumstances.

Holemobility in polyfluorene/fullerene blends has been studied with field effecttransistors. Two different C60 derivatives and one C70 derivative havebeen investigated together with two different polyfluorenes. Mobility is presentedas a function of acceptor loading at ratios suitable forphotovoltaics and varies between 10–3 and 10–5 cm2 V–1 s–1 depending on thepolymer/acceptor combination. The hole mobility is increased in blends withthe commonly used acceptor [6-6]-phenyl-C61-butyric acid methylester (PCBM). With relatedC60 and C70 derivatives the hole mobility is decreased underthe same circumstances.

Non-ideal behavior in organic field effect transistors, in particular threshold voltage drift and light sensitivity, is argued to be due to intrinsic carrier dynamics. The discussion is based on the theory for hopping transport within a Gaussian density of states. Carrier concentration is shown to be of fundamental importance, and the time required to reach equilibrium at different bias is responsible for device behavior, with implications for mobility evaluation. Experimental results from various conjugated polymers in a field effect transistor illustrate the theory.

Bothelectron and hole mobilities have been simultaneously measured through chargeextraction by linearly increasing voltage on polymer heterojunction solar cellswith varying stoichiometry of polymer and acceptor. The polymer isa low band gap copolymer of fluorene, thiophene, and electronaccepting groups named APFO-Green 5, and the acceptor is [6,6]-phenyl-C61-butyricacid methylester. Results are correlated to field effect transistor measurementson the same material system. A monotonous increase in mobilityfor both carrier types is observed with increased acceptor loading.

Bipolartransport in blends of a copolymer of fluorene, thiophene andelectron accepting groups, and the substituted fullerene [6,6]-phenyl-C61-butyric acid methylesterhave been studied through charge extraction by linearly increasing voltageon solar cells and with field effect transistors. Between 10%and 90% polymer has been used and the results showa clear correlation to solar cell performance. Optimal solar cellscomprise 20% polymer and have a power conversion efficiency of3.5%. The electron mobility is increasing strongly with fullerene content,but is always lower than the hole mobility, thus explainingthe low amount of polymer in optimized devices.

Temperature dependent charge carrier mobility measurements using field effect transistors and density functional theory calculations are combined to show how the conformation dependent frontier orbital delocalization influences the hole-and electron mobilities in a donor-acceptor based polymer. A conformationally sensitive lowest unoccupied molecular orbital results in an electron mobility that decreases with increasing temperature above room temperature, while a conformationally stable highest occupied molecular orbital is consistent with a conventional hole mobility behavior and also proposed to be one of the reasons for why the material works well as a hole transporter in amorphous bulk heterojunction solar cells.

Different mixtures of identically substituted C60 and C70 based fullerens have been used as acceptors in three polymer: fullerene systems that strongly express various performance limiting aspects of bulk heterojunction solar cells. Results are correlated with, and discussed in terms of e.g. morphology, charge separation, and charge transport. In these systems, there appears to be no relevant differences in either mobility or energy level positions between the identically substituted C60 and C70 based fullerenes tested. Examples of how fullerene mixtures influence the nano-morphology of the active layer are given. An upper limit to the open circuit voltage that can be obtained with fullerenes is also suggested.

We combine results from transient optical absorption in a bulk heterojunction polymer donor/fullerene acceptor material, obtained in the optical range as well as in the THz range, with results from electrical transients after a short light pulse, to present a unified interpretation of the transport of charge after the very first act of photoinduced charge transfer. We find that the mobility of charges is initially very high, but dramatically reduced with time, to arrive at values three orders of magnitude lower. We show that this can be understood as a consequence of the transport of hot charges by hopping through the density of states, from higher to lower energies.

Recombination in the well-performing bulk heterojunction solar cell blend between the conjugated polymer TQ-1 and the substituted fullerene PCBM has been investigated with pump-probe transient absorption and charge extraction of photo-generated carriers (photo-CELIV). Both methods are shown to generate identical and overlapping data under appropriate experimental conditions. The dominant type of recombination is bimolecular with a rate constant of 7 x 10(-12) cm(-3) s(-1). This recombination rate is shown to be fully consistent with solar cell performance. Deviations from an ideal bimolecular recombination process, in this material system only observable at high pump fluences, are explained with a time-dependent charge-carrier mobility, and the implications of such a behavior for device development are discussed.

Empirical data for the fill factor as a function of charge carrier mobility for two different polymer: fullerene systems is presented and analyzed. The results indicate that charge extraction depth limitations and space charge effects are inconsistent with the observed behavior, and the decrease in the fill factor is, instead, attributed to the field-dependent charge separation and geminate recombination. A solar cell photocurrent limited by the Onsager-Braun charge transfer exciton dissociation is shown to be able to accommodate the experimental observations. Charge dissociation limited solar cells always benefit from increased mobilities, and the negative contribution from the reduced charge separation is shown to be much more important for the fill factor in these material systems than any adverse effects from charge carrier extraction depth limitations or space charge effects due to unbalanced mobilities. The logarithmic dependence of the fill factor on the mobility for such a process is also shown to imply that simply increasing the mobilities is an impractical way to reach very high fill factors under these conditions since unrealistically high mobilities are required. A more controlled morphology is, instead, argued to be necessary for high performance.

We present the synthesis and characterisation of poly(2-(2',5'-bis(2?-ethylhexyloxy)phenyl)-1, 4-phenylenevinylene) (BEHP-PPV) polymerised under different conditions. The photoluminescence efficiencies (?PL) in the solid state of BEHP-PPV obtained at 144°C and 0°C are 28% and 60%, respectively. Polymerisation temperatures below 0°C decreases the molecular weight without changing the photoluminescence efficiency to any large extent.

Organic solar cells using carbon based materials have the potential to deliver cheap solar electricity. The aim is to be able to produce solar cells with common printing techniques on flexible substrates, and as organic materials can be made soluble in various solvents, they are well adapted to such techniques. There is a large variation of organic materials produced for solar cells, both small molecules and polymers. Alterations of the molecular structure induce changes of the electrical and optical properties, such as band gap, mobility and light absorption. During the development of organic solar cells, the step of mixing of an electron donor and an electron acceptor caused a leap in power conversion efficiency improvement, due to an enhanced exciton dissociation rate. Top performing organic solar cells now exhibit a power conversion efficiency of over 10%. Currently, a mix of a conjugated polymer, or smaller molecule, and a fullerene derivative are commonly used as electron donor and acceptor. Here, the blend morphology plays an important role. Excitons formed in either of the donor or acceptor phase need to diffuse to the vicinity of the donor-acceptor interface to efficiently dissociate. Exciton diffusion lengths in organic materials are usually in the order of 5-10 nm, so the phases should not be much larger than this, for good exciton quenching. These charges must also be extracted, which implies that a network connected to the electrodes is needed. Consequently, a balance of these demands is important for the production of efficient organic solar cells.

Morphology has been found to have a significant impact on the solar cell behaviour and has thus been widely studied. The aim of this work has been to visualize the morphology of active layers of organic solar cells in three dimensions by the use of electron tomography. The technique has been applied to materials consisting of conjugated polymers blended with fullerene derivatives. Though the contrast in these blends is poor, three-dimensional reconstructions have been produced, showing the phase formation in three dimensions at the scale of a few nanometres. Several material systems have been investigated and preparation techniques compared.

Even if excitons are readily dissociated and paths for charge extraction exist, the low charge mobilities of many materials put a limit on film thickness. Although more light could be absorbed by increased film thickness, performance is hampered due to increased charge recombination. A large amount of light is thus reflected and not used for energy conversion. Much work has been put into increasing the light absorption without hampering the solar cell performance. Aside from improved material properties, various light trapping techniques have been studied. The aim is here to increase the optical path length in the active layer, and in this way improve the absorption without enhanced extinction coefficient.

At much larger dimensions, light trapping in solar cells with folded configuration has been studied by the use of optical modelling. An advantage of these V-cells is that two materials with complementing optical properties may be used together to form a tandem solar cell, which may be connected in either serial or parallel configuration, with maintained light trapping feature. In this work optical absorption in V-cells has been modelled and compared to that of planar ones.

Abstract [en]

Electron tomography has been used for analyzing the active layer in a polymer solar cell, a bulk heterojunction of an alternating copolymer of fluorene and a derivative of fullerene. The method supplies a three-dimensional representation of the morphology of the film, where domains with different scattering properties may be distinguished. The reconstruction shows good contrast between the two phases included in the film and demonstrates that electron tomography is an adequate tool for investigations of the three-dimensional nanostructure of the amorphous materials used in polymer solar cells.

Abstract [en]

Control of the nanoscale morphology of the donor-acceptor material blends inorganic solar Cells is critical for optimizing the photovoltaic performances. The influence of intrinsic (acceptor materials) and extrinsic (donor:acceptor weight ratio, substrate, solvent) parameters was investigated, by atomic force microscopy (AFM) and electron tomography (ET), on the nanoscale phase separation of blends of a low-band-gap alternating polyfluorene copolymers (APFO-Green9) with [6,6]-phenyl-C-71-butyric acid methyl ester ([70]PCBM). The photovoltaic performances display an optimal efficiency for the device elaborated with a 1:3 APFO-Green polymer:[70][PCBM weight ratio and spin-coated from chloroform solution. The associated active layer morphology presents small phase-separated domains which is a good balance between as a large interfacial donor-acceptor area and Continuous paths of the donor and acceptor phases to the electrodes.

Abstract [en]

How 1,8-diiodooctane (DIO) enhances performance of polymer solar cells based on polymer HXS-1 and fullerene [6,6]-phenyl C(71)-butyric acid methyl ester (PC(71)BM) from 3.6% to 5.4% is scrutinized with several techniques by comparing devices or blend films spin-coated from dichlorobenzene (DCB) to those from DCB/DIO (97.5:2.5 v/v). Morphology of blend films is examined with atomic force microscopy (AFM), transmission electron microscopy (TEM) and electron tomography (3-D TEM), respectively. Charge generation and recombination is studied with photoluminescence, and charge transport with field effect transistors. The morphology with domain size in 10-20 nm and vertical elongated clusters formed in DIO system is supposed to facilitate charge transport and minimize charge carrier recombination, which are the main reasons for enhancing power conversion efficiency (PCE) from 3.6% (without DIO) to 5.4% (with DIO). Furthermore, a two year inspection shows no significant impact of DIO on the shelf-stability of the solar cells. No visible degradation in the second year indicates that the morphology of the active layers in the devices is relatively stable after initial relaxation in the first year.

Abstract [en]

In this study, it is demonstrated that a finer nanostructure produced under a rapid rate of solvent removal significantly improves charge separation in a high-performance polymer: fullerene bulk-heterojunction blend. During spin-coating, variations in solvent evaporation rate give rise to lateral phase separation gradients with the degree of coarseness decreasing away from the center of rotation. As a result, across spin-coated thin films the photocurrent at the first interference maximum varies as much as 25%, which is much larger than any optical effect. This is investigated by combining information on the surface morphology of the active layer imaged by atomic force microscopy, the 3D nanostructure imaged by electron tomography, film formation during the spin coating process imaged by optical interference and photocurrent generation distribution in devices imaged by a scanning light pulse technique. The observation that the nanostructure of organic photovoltaic blends can strongly vary across spin-coated thin films will aid the design of solvent mixtures suitable for high molecular-weight polymers and of coating techniques amenable to large area processing.

Abstract [en]

Several organic materials and blends have been studied with the use of electron tomography. Tomography reconstructions of active layers of organic solar cells, where various preparation techniques have been used, have been analysed and compared to device behaviour. In addition, materials with predefined structures, including contrast enhancing features, have been studied and double tilt data collection has been employed to improve reconstructions. Small changes in preparation procedures may lead to large differences in morphology and device performance, and the results also indicate a complex relation between these.

Abstract [en]

The optical behavior of a reflective tandem solar cell (V cell) is modeled by means of finite element method (FEM) simulations. The absorption of solar light in the active material as well as in both electrode layers is calculated. The FEM solves the electromagnetic wave equation on the entire defined geometry, resulting in the consideration of interference effects, as well as effects of refraction and reflection. Both single cells and tandem cells are modeled and confirmed to be in accordance with reflectance measurements. Energy dissipation in the active layers is studied as a function of layer thickness and folding angle, and the simulations clearly display the advantage of the light trapping feature of folded cells. This is especially prominent in cells with thinner active layers, where folding induces absorption in the active layer equivalent to that of much thicker cells.

Abstract [en]

Optical modeling of one folded tandem solar cell and four types of stacked tandem solar cells has been performed using the finite element method and the transfer matrix method for the folded cell and the stacked cells, respectively. The results are analyzed by comparing upper limits for short circuit currents and power conversion efficiencies. In the case of serial connected tandems all of the five cell types may be compared, and we find that the folded cells are comparable to stacked tandem cells in terms of currents and power conversion efficiencies.

Abstract [en]

Folded and planar solar cells are examined with optical simulations, with the finite element method. The maximum photocurrent densities during the full day are compared between cells of different geometries and tilting angles. The change of incident angle and spectrum over time are handled in this analysis. The results show that the light trapping effect of the folded cell makes these cells show higher maximum photocurrent densities than the planar cells during all hours of the day. This is the case for both single and tandem cells. The results also indicate that balancing the currents in the tandem cells by adjusting the active layer thickness may be more cumbersome with the folded tandem cells than the stacked planar cells.

Abstract [en]

The role of an optical spacer layer has been examined by optical simulations of organic solar cells with various bandgaps. The simulations have been performed with the transfer matrix method and the finite element method. The results show that no beneficial effect can be expected by adding an optical spacer to a solar cell with an already optimized active layer thickness.

Electron tomography has been used for analyzing the active layer in a polymer solar cell, a bulk heterojunction of an alternating copolymer of fluorene and a derivative of fullerene. The method supplies a three-dimensional representation of the morphology of the film, where domains with different scattering properties may be distinguished. The reconstruction shows good contrast between the two phases included in the film and demonstrates that electron tomography is an adequate tool for investigations of the three-dimensional nanostructure of the amorphous materials used in polymer solar cells.

The role of an optical spacer layer has been examined by optical simulations of organic solar cells with various bandgaps. The simulations have been performed with the transfer matrix method and the finite element method. The results show that no beneficial effect can be expected by adding an optical spacer to a solar cell with an already optimized active layer thickness.

Several organic materials and blends have been studied with the use of electron tomography. Tomography reconstructions of active layers of organic solar cells, where various preparation techniques have been used, have been analysed and compared to device behaviour. In addition, materials with predefined structures, including contrast enhancing features, have been studied and double tilt data collection has been employed to improve reconstructions. Small changes in preparation procedures may lead to large differences in morphology and device performance, and the results also indicate a complex relation between these.

Optical modeling of one folded tandem solar cell and four types of stacked tandem solar cells has been performed using the finite element method and the transfer matrix method for the folded cell and the stacked cells, respectively. The results are analyzed by comparing upper limits for short circuit currents and power conversion efficiencies. In the case of serial connected tandems all of the five cell types may be compared, and we find that the folded cells are comparable to stacked tandem cells in terms of currents and power conversion efficiencies.

A method to prepare amyloid-like fibrils functionalized with magnetic nanoparticles has been developed. The amyloid-like fibrils are prepared in a two step procedure, where insulin and magnetic nanoparticles are mixed simply by grinding in the solid state, resulting in a water soluble hybrid material. When the hybrid material is heated in aqueous acid, the insulin/nanoparticle hybrid material self assembles to form amyloid-like fibrils incorporating the magnetic nanoparticles. This results in magnetically labeled amyloid-like fibrils which has been characterized by Transmission Electron Microscopy (TEM) and electron tomography. The influence of the aggregation process on proton relaxivity is investigated. The prepared materials have potential uses in a range of bio-imaging applications.

The optical behavior of a reflective tandem solar cell (V cell) is modeled by means of finite element method (FEM) simulations. The absorption of solar light in the active material as well as in both electrode layers is calculated. The FEM solves the electromagnetic wave equation on the entire defined geometry, resulting in the consideration of interference effects, as well as effects of refraction and reflection. Both single cells and tandem cells are modeled and confirmed to be in accordance with reflectance measurements. Energy dissipation in the active layers is studied as a function of layer thickness and folding angle, and the simulations clearly display the advantage of the light trapping feature of folded cells. This is especially prominent in cells with thinner active layers, where folding induces absorption in the active layer equivalent to that of much thicker cells.

Folded and planar solar cells are examined with optical simulations, with the finite element method. The maximum photocurrent densities during the full day are compared between cells of different geometries and tilting angles. The change of incident angle and spectrum over time are handled in this analysis. The results show that the light trapping effect of the folded cell makes these cells show higher maximum photocurrent densities than the planar cells during all hours of the day. This is the case for both single and tandem cells. The results also indicate that balancing the currents in the tandem cells by adjusting the active layer thickness may be more cumbersome with the folded tandem cells than the stacked planar cells.

A mesoscopic network in the form of a hydrogel of the highly conductive polymer PEDOT/PSS hydrogel was used in an enzyme electrode setup. Osmium was used both as a crosslink point in the hydrogel network and as a mediator between the prosthetic group of the enzyme and the conductive polymer matrix. Both biostability and high conductivity is important aspects when building nerve- or cell- electrodes. Diffusion of analytes surrounding the cells into the matrix electrode is feasible due to the open hydrogel structure. The high water content in these structures is important when buffering them to a pH of choice.

Electrodes coated with the conducting polymer poly(3,4-ethylene dioxythiophene) (PEDOT) possess attractive electrochemical properties for stimulation or recording in the nervous system. Biomolecules, added as counter ions in electropolymerization, could further improve the biomaterial properties, eliminating the need for surfactant counter ions in the process. Such PEDOT/biomolecular composites, using heparin or hyaluronic acid, have previously been investigated electrochemically. In the present study, their biocompatibility is evaluated. An agarose overlay assay using L929 fibroblasts, and elution and direct contact tests on human neuroblastoma SH-SY5Y cells are applied to investigate cytotoxicity in vitro. PEDOT: heparin was further evaluated in vivo through polymer-coated implants in rodent cortex. No cytotoxic response was seen to any of the PEDOT materials tested. The examination of cortical tissue exposed to polymer-coated implants showed extensive glial scarring irrespective of implant material (Pt:polymer or Pt). However, quantification of immunological response, through distance measurements from implant site to closest neuron and counting of ED1+ cell density around implant, was comparable to those of platinum controls. These results indicate that PEDOT: heparin surfaces were non-cytotoxic and show no marked difference in immunological response in cortical tissue compared to pure platinum controls.

New strategies to improve neuron coupling to neuroelectronic implants are needed. In particular, tomaintain functional coupling between implant and neurons, foreign body response like encapsulation must meminimized. Apart from modifying materials to mitigate encapsulation it has been shown that with extremely thinstructures, encapsulation will be less pronounced. We here utilize wire electrochemical transistors (WECTs) usingconducting polymer coated fibers. Monofilaments down to 10 μm can be successfully coated and weaved intocomplex networks with built in logic functions, so called textile logic. Such systems can control signal patterns at alarge number of electrode terminals from a few addressing fibres. Not only is fibre size in the range where lessencapsulation is expected but textiles are known to make successful implants because of their soft and flexiblemechanical properties. Further, textile fabrication provides versatility and even three dimensional networks arepossible. Three possible architectures for neuroelectronic systems are discussed. WECTs are sensitive to dehydrationand materials for better durability or improved encapsulation is needed for stable performance in biologicalenvironments.

Development of electroactive conjugated polymers, for the purpose of recording and eliciting signals in the neural systems in humans, can be used to fashion the interfaces between the two signalling systems of electronics and neural systems. The design of desirable chemical, mechanical and electrical properties in the electroactive polymer electrodes, and the means of integration of these into biological systems, are here reviewed.

Electrodes intended for neural communication must be designed to meet both the electrochemical and biological requirements essential for long term functionality. Metallic electrode materials have been found inadequate to meet these requirements and therefore conducting polymers for neural electrodes have emerged as a field of interest. One clear advantage with polymer electrodes is the possibility to tailor the material to have optimal biomechanical and chemical properties for certain applications. To identify and evaluate new materials for neural communication electrodes, three charged biomolecules, fibrinogen, hyaluronic acid (HA), and heparin are used as counterions in the electrochemical polymerization of poly (3,4-ethylenedioxythiophene) (PEDOT). The resulting material is evaluated electrochemically and the amount of exposed biomolecule on the surface is quantified. PEDOT: biomolecule surfaces are also studied with static contact angle measurements as well as scanning electron microscopy and compared to surfaces of PEDOT electrochemically deposited with surfactant counterion polystyrene sulphonate (PSS). Electrochemical measurements show that PEDOT: heparin and PEDOT: HA, both have the electrochemical properties required for neural electrodes, and PEDOT: heparin also compares well to PEDOT: PSS. PEDOT: fibrinogen is found less suitable as neural electrode material.

A promising fabrication method of electron transporting interlayers for solution-processed optoelectronic devices by electrophoretic deposition (EPD) of colloidal zinc oxide (ZnO) nanocrystals was demonstrated. A low voltage of 3-5 V and a short deposition time of 40 s at room temperature were found to be sufficient to generate dense and uniform ZnO thin films. The EPD ZnO nanocrystal films were applied as ETLs for inverted organic solar cell and polymer light emitting diodes (PLEDs). By optimizing the EPD processing of ZnO nanocrystal electron transporting layers (ETLs), inverted organic solar cells based on [3,4-b]-thiophene/benzodithiophene (PTB7): [6-6]-phenyl-C71-butyric acid methyl ester (PC71BM) and poly(3-hexylthiophene) (P3HT): [6-6]-phenyl-C-61-butyric acid methyl ester (PC61BM) with an average PCE of 8.4% and 4.0% were fabricated. In combination with the PLEDs and flexible devices results, we conclude that the EPD processed ZnOnanocrystal thin films can serve as high quality ETLs for solution-processed optoelectronic devices.

The surface defects of solution-processed ZnO films lead to various intragap states. When the solution-processed ZnO films are used as electron transport interlayers (ETLs) in inverted organic solar cells, the intragap states act as interfacial recombination centers for photogenerated charges and thereby degrade the device performance. Here, a simple passivation method based on ethanedithiol (EDT) treatment is demonstrated, which effectively removes the surface defects of the ZnO nanocrystal films by forming zinc ethanedithiolates. The passivation by EDT treatment modulates the intragap states of the ZnO films and introduces a new intragap band. When the EDT-treated ZnO nanocrystal films are used as ETLs in inverted organic solar cells, both the power conversion efficiency and stability of the devices are improved. The control studies show that the solar cells with EDT-treated ZnO films exhibit reduced charge recombination rates and enhanced charge extraction properties. These features are consistent with the fact that the modulation of the intragap states results in reduction of interfacial recombination as well as the improved charge selectivity and electron transport properties of the ETLs. It is further demonstrated that the EDT treatment-based passivation method can be extended to ZnO films deposited from sol-gel precursors.